CN1118540C - Process for dearsenicating hydrocarbon oil - Google Patents
Process for dearsenicating hydrocarbon oil Download PDFInfo
- Publication number
- CN1118540C CN1118540C CN 99119666 CN99119666A CN1118540C CN 1118540 C CN1118540 C CN 1118540C CN 99119666 CN99119666 CN 99119666 CN 99119666 A CN99119666 A CN 99119666A CN 1118540 C CN1118540 C CN 1118540C
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- CN
- China
- Prior art keywords
- carrier
- sorbent material
- active ingredient
- arsenic
- zinc
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a dearsenization adsorbent which is composed of active ingredients and a carrier, wherein the carrier is selected from at least one kind or a plurality of kinds of free active oxides (gamma-Al2O3, beta-Al2O3, eta-Al2O3, theta-Al2O3), titanium dioxide, silicon oxide and aluminum oxide or a mixture thereof; the active ingredients are selected from at least one kind or a plurality of kinds of free copper (zinc) oxide (sulfuret), sulfate (copper oxide, zinc oxide, copper sulfide, zinc sulfide, cupric sulfate and zinc sulfate) or a mixture thereof; if the total weight of the adsorbent is used as a reference, the active ingredients account for 1 to 20 wt%, and the carrier accounts for 80 to 99 wt%. The present invention also provides a method for eliminating arsenic (arsine) from hydrocarbon oil.
Description
The present invention relates to a kind of method that removes arsenic.More particularly, the present invention relates to use the sorbent material of forming by active ingredient and carrier, from the hydrocarbon ils of sulfur-bearing and arsenic, remove the method for arsenic.
As everyone knows, the heavy metal arsenic that contains in hydrocarbon ils such as the petroleum naphtha produces many injurious effects to the deep processing of hydrocarbon ils.Process catalyst is poisoned, be deposited on the surface of processing unit and pipe fitting etc., cause coking, reduced output and economic benefit, when serious, even technological process can not be carried out.Therefore, the arsenic content in the stock oil there is strict regulation, for example, 20-2000ppb.In order to remove arsenic, people have carried out research chronically, have proposed various arsenic removing methods.
United States Patent (USP) 3782076,3789871,3542669 and 4849577 all relates to is not having to remove arsenic in the presence of the organosulfur.
The used sorbent material of arsenic removal comprises for example PbO/Al
2O
3, CuO/ γ-Al
2O
3, CuO/ZnO/ γ-Al
2O
3
United States Patent (USP) 4593148 discloses the method for removing arsine from the air-flow that contains arsine and hydrogen sulfide.This method is that described air-flow is contacted with the sorbent material of being made up of cupric oxide and zinc oxide.Described sorbent material is to be prepared by coprecipitation method or pickling process.
United States Patent (USP) 5169516 discloses a kind of method of removing arsenic from the liquid stream that contains arsenic and sulfide.This method is arsenic removal after the first desulfurization, and the used sorbent material of arsenic removal is not contain or the low γ-Al that contains
2O
3Cupric oxide or zinc oxide dearsenification sorbent material.
The inventor compares arsenic removal (arsine) method and the used sorbent material of prior art, at problems of the prior art, study chronically and test, found a kind of arsenic removal that not influenced by sulfide (arsine) sorbent material and arsenic removal (arsine) method.This method is with dearsenification sorbent material such as CuSO
4/ Al
2O
3, the arsenic in the hydrocarbon oil crude material (arsine) is reduced to less than 10ppb from 300ppb.
Therefore, the purpose of this invention is to provide a kind of dearsenification (arsine) sorbent material, be used for removing the arsenic (arsine) of hydrocarbon ils logistics.
Another object of the present invention provides a kind of arsenic removal (arsine) method.
Dearsenification of the present invention (arsine) sorbent material is made up of active ingredient and carrier.Described active ingredient is selected from the oxygen (sulphur) of copper (zinc) and changes thing or vitriol, for example, and at least a in cupric oxide, zinc oxide, zinc sulphide, cupric sulfide, copper sulfate, zinc sulfate or its mixture.Described carrier is selected from activated alumina, and for example, it is selected from γ-Al
2O
3, β-Al
2O
3, η-Al
2O
3, θ-Al
2O
3Or at least a in a kind of, the titanium dioxide in its mixture, silicon-dioxide-aluminium sesquioxide or their mixture.Activated alumina can prepare with diaspore calcination under 400 ℃ of-800 ℃ of temperature.The specific surface area of activated alumina is 150-250m
2/ g, pore size distribution are 10-200 , and total pore volume is 0.4-1.0ml/g, crushing strength be greater than 0.2 newton/.
Activated alumina is added an amount of (about 10 weight %-are in the weight of activated alumina) nitric acid or hydrochloric acid, an amount of water (about 29 weight %-in activated alumina weight) to the preparation method of the carrier that dearsenification of the present invention (arsine) sorbent material is used and an amount of pore-forming material and additive made thick, be shaped to strip or granular with method well known in the art, be generally φ 2mm-φ 5mm.Dry back in 120 ℃ 400-800 ℃ of calcination.
Dearsenification of the present invention (arsine) preparation of adsorbent method is by proportioning active ingredient to be made the aqueous solution, and an amount of carrier is immersed in the made solution, after 100-120 ℃ of drying, gets final product in the calcination in airflow of 400-800 ℃ temperature.The method of dipping is that those skilled in that art are known, available dry immersion, and also available soak law, also available spraying method is held on the carrier as long as active ingredient can be carried.Active ingredient is carried the amount that is held on the carrier and is generally 1-20 weight %, is preferably 5-15 weight %, 7-13 weight % more preferably, and surplus is a carrier.
Arsenic (arsine) capacity of dearsenification of the present invention (arsine) sorbent material is more than 0.8% (weight), and life cycle was at least 1 year.
The active evaluation test of dearsenification (arsine) sorbent material is to carry out in fixed-bed reactor.Its test conditions is:
Catalyzer loading amount 100ml (granular, Φ 2-3mm)
The stock oil petroleum naphtha
Temperature 30-110 ℃ of dearsenification (arsine)
Adsorption bed working pressure normal pressure-3.0Mpa
Air speed 1-4h
-1
Dearsenification of the present invention (arsine) sorbent material use for some time or by arsenic (arsine) saturated after, can regenerate.Its regeneration condition is:
Regeneration temperature 200-400 ℃
Resurgent gases nitrogen air speed 500-2000h
-1
The quality of used petroleum naphtha is as follows in the test:
Proportion 0.71-0.76
Boiling range ℃
Initial boiling point 46
50％ 99
90％ 129
Do 203
Arsenic (ppb) 300
Sulphur (mg/l) 132
Describe the present invention further below by embodiment, the present invention is more in depth understood with promotion.But the present invention is not subjected to the restriction of these embodiment.Those skilled in the art can make amendment or improve under the guide of spirit of the present invention the present invention, all belong to apparent.Propose in protection scope of the present invention appended claims book below.
Embodiment 1
Preparing carriers I:
With the known coprecipitation method of crowd, be about to make titanium hydroxide in the ammonium hydroxide adding titanium tetrachloride, after the washing drying, under 500 ℃ of-600 ℃ of temperature, the roasting decomposition obtains titanium dioxide.Adding pore-forming material, binding agent carry out moulding, and obtaining specific surface area is 150-200m
2/ g, pore volume are the carrier (I type) of 0.5-0.7ml/g.
Preparing carriers II:
Make aluminium hydroxide with coprecipitation method.Add nitric acid or polyoxyethylene glycol or molecular weight and be 10000 stick, make ball or column.400 ℃ of-500 ℃ of temperature roastings, obtain specific surface 180-200m then
2/ g, pore volume are the carrier (II type) of 0.7-0.9ml/g.
Preparing carriers III:
With commercially available activated alumina or aluminium oxide-silicon oxide ball, through water vapor or add expanding agent and handle, obtain the carrier (III type) of institute's palpus.
Embodiment 2
Preparation of Catalyst I-pickling process
Take by weighing each 1000 gram of I type, II type and III type carrier, immerse 800ml, concentration is in the copper sulfate solution of 15 weight %, soak and dry after doing, dry back makes C-I type, C-II type and C-III type catalyzer in 400 ℃ of roastings under 120 ℃ of temperature.
Preparation of Catalyst II-spraying method
Adopt spraying method, make C-IV type, C-V type C-VI type catalyzer by the condition among the Preparation of Catalyst I.
Embodiment 3
The activity rating of catalyst test:
Evaluation test 1
Get any catalyzer 100ml (granular Φ 2-3mm) of above-mentioned preparation, the fixed-bed reactor of the Φ 20 * 1000mm that packs into.Under envrionment temperature and normal pressure, press 2.0h
-1The air speed feeding contains arsenic 200ppb and sulfur-bearing is the petroleum naphtha of 134ppm, and its experimental result is as follows:
Time (hour) outlet arsenic (ppb)
40 1
88 6.5
160 6.9
208 8.5
256 8.8
Evaluation test 2
Use following dearsenification condition: pressure is 3.0h as 3.0Mpa, air speed
-1With temperature be 50 ℃, 70 ℃, 90 ℃, ℃ 110, other is identical with evaluation test 1 to carry out dearsenification, its test-results is as follows:
Time (hour) outlet arsenic (ppb)
50℃ 70℃ 90℃ 110℃
42 7.3 5.7 1.2 ＜1
66 5.4 4.1 1.6 ＜1
90 10.2 4.8 1.4 ＜0.5
114 12 4.2 1.1 ＜1
138 8.9 3.5 1.3 ＜1
162 9.5 5.3 1.2 ＜1
234 10 4.4 2.0 ＜1
282 - 4.7 2.1 ＜1
306 - ＜1 1.7 ＜1
330 - 3.9 3.8 ＜1
Evaluation test 3
In temperature is that 70 ℃, pressure are that 3.0Mpa, air speed are 3h
-1With petroleum naphtha to contain arsenic be 200ppb with the sulfur-bearing condition that to be 134ppm and other identical with evaluation test 1 under, carry out the dearsenification test.Measure sulphur content in the oil of reaction back simultaneously.Its test is as follows:
Time (hour) sulphur content (mg/l)
24 123
48 133
96 123
Embodiment 4 regeneration tests
After with the petroleum naphtha that contains arsenic 1000ppb catalyzer being quickened poisoning and deactivation, carry out manipulation of regeneration.
Get decaying catalyst 500ml, in the regenerating tube of packing into, with 600h
-1Air speed feeds nitrogen.Under 350 ℃ of temperature, purge the organism in the sorbent material.After no longer including organism in the tail gas, under the constant condition of air speed, allocate the air of 1 volume % into, occur this moment heating up.Regulate air flow quantity, keep that temperature rise is the highest to be no more than 450 ℃.No longer heat up when increasing air capacity again, i.e. regeneration is finished.
Catalyzer after the regeneration is packed in the reactor, is that 50 ℃, pressure are 3.0h for normal, air speed in temperature
-1Contain under the condition that arsenic is 200ppb with petroleum naphtha, carry out the dearsenification test.Its result is as follows:
Time (hour) outlet arsenic (ppb)
22 7.3
70 5.4
118 16.0
238 18.4
310 16.7
400 17.1
Embodiment 5
After will using 3200 hours, the catalyst segments of arsenic-removing rate 90% is measured the arsenic content on the different catalysts bed.
Catalyst bed arsenic content (weight %)
Inlet 0.9
The bed in 0.5
Outlet 0.1
Claims (9)
1. method that from petroleum naphtha, removes arsenic, the feature of this method is that petroleum naphtha is contacted with the sorbent material of being made up of active ingredient and carrier, described active ingredient is selected from by cupric oxide, zinc oxide, cupric sulfide, or their mixture, zinc sulphide, copper sulfate, at least a or several in zinc sulfate or their the mixture composition group, described carrier is selected from by activated alumina, titanium dioxide, at least a or several in silicon-dioxide-aluminium sesquioxide or their the mixture composition group, gross weight in sorbent material, active ingredient is 1-20 weight %, and surplus is a carrier.
2. by the method for claim 1, it is characterized in that described activated alumina is selected from by γ-Al
2O
3, β-Al
2O
3, η-Al
2O
3, θ-Al
2O
3Or at least a or several in their the mixture composition group.
3. by the method for claim 1, the surface-area that it is characterized in that described activated alumina is 150-250m
2/ g, the effective pore radius is 10-100 , total pore volume is 0.4-1.0ml/g.
4. by the method for claim 1, it is characterized in that it is 5-15 weight % that sorbent material contains active ingredient, all the other are carrier.
5. by the method for claim 1, the active ingredient that it is characterized in that sorbent material is a copper sulfate, and carrier is γ-Al
2O
3
6. by the method for claim 1, the active ingredient that it is characterized in that sorbent material is copper sulfate and cupric sulfide, and carrier is γ-Al
2O
3
7. by the method for claim 1, the active ingredient that it is characterized in that sorbent material is cupric oxide and zinc oxide, and carrier is γ-Al
2O
3
8. by the method for claim 1, it is characterized in that the sorbent material immersion process for preparing.
9. by the method for claim 1, it is characterized in that sorbent material prepares with spraying method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119666 CN1118540C (en) | 1999-09-24 | 1999-09-24 | Process for dearsenicating hydrocarbon oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119666 CN1118540C (en) | 1999-09-24 | 1999-09-24 | Process for dearsenicating hydrocarbon oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289820A CN1289820A (en) | 2001-04-04 |
| CN1118540C true CN1118540C (en) | 2003-08-20 |
Family
ID=5281026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99119666 Expired - Fee Related CN1118540C (en) | 1999-09-24 | 1999-09-24 | Process for dearsenicating hydrocarbon oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1118540C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005042130A1 (en) * | 2003-10-31 | 2005-05-12 | Metal Alloy Reclaimers, Inc Ii | Process for reduction of inorganic contaminants from waste streams |
| CN1297634C (en) * | 2004-09-02 | 2007-01-31 | 中国石油化工股份有限公司 | Method for removing arsenide from liquid hydrocarbon |
| CN101472678A (en) * | 2006-06-21 | 2009-07-01 | 巴斯夫欧洲公司 | Absorption composition and process for removing mercury |
| CN100441294C (en) * | 2007-05-10 | 2008-12-10 | 湖北省化学研究院 | Deovo catalyst for raw gas of carbon monoxide, preparation, and application |
| GB0802828D0 (en) * | 2008-02-15 | 2008-03-26 | Johnson Matthey Plc | Absorbents |
| CN103394324B (en) * | 2013-08-07 | 2015-01-28 | 沈阳三聚凯特催化剂有限公司 | Load-type dearsenic agent and preparation method |
| GB201509822D0 (en) * | 2015-06-05 | 2015-07-22 | Johnson Matthey Plc | Method for preparing a sorbent |
| GB201509823D0 (en) * | 2015-06-05 | 2015-07-22 | Johnson Matthey Plc | Method for preparing a sorbent |
| CN106833731B (en) * | 2017-03-17 | 2018-04-20 | 钦州学院 | A kind of hydro-dearsenic method of naphtha |
| CN113426404B (en) * | 2021-06-22 | 2023-11-17 | 南京水滴环境工程有限公司 | Preparation method of arsenic removal medicament for organophosphorus pesticide wastewater |
-
1999
- 1999-09-24 CN CN 99119666 patent/CN1118540C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1289820A (en) | 2001-04-04 |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030820 Termination date: 20170924 |
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| CF01 | Termination of patent right due to non-payment of annual fee |